Novel organoleptic compounds

ABSTRACT

The present invention relates to the novel use of (oxybis)dicyclohexane compounds as fragrance materials.

STATUS OF RELATED APPLICATION

This application claims priority to U.S. Provisional Patent ApplicationNo. 62/436,523, filed Dec. 20, 2016, the contents hereby incorporated byreference as if set forth in its entirety.

FIELD OF THE INVENTION

The present invention relates to new chemical entities and theincorporation and use of the new chemical entities as fragrancematerials.

BACKGROUND OF THE INVENTION

There is an ongoing need in the fragrance industry to provide newchemicals to give perfumers and other persons the ability to create newfragrances for perfumes, colognes and personal care products. Those withskill in the art appreciate how differences in the chemical structure ofthe molecule can result in significant differences in the odor, notesand characteristics of a molecule. These variations and the ongoing needto discover and use the new chemicals in the development of newfragrances allow the perfumers to apply the new compounds in creatingnew fragrances.

SUMMARY OF THE INVENTION

The present invention provides the unexpected novel use of(oxybis)dicyclohexane compounds in enhancing, improving or modifying thefragrance of perfumes, colognes, toilet water, fabric care products,personal products and the like.

Specifically, the present invention relates to (oxybis)dicyclohexanecompounds represented by Formula I set forth below:

wherein R¹ and R² are identical or different and each is a C₁-C₃alkylene group; R³ and R⁴ are identical or different and each ishydrogen or methyl located in any positions of the ring to which theyare attached; and wherein m and n are identical or different and each isan integer of 0 or 1.

Another embodiment of the present invention relates to a subgenus of theabove (oxybis)dicyclohexane compounds represented by Formula II setforth below:

wherein R¹, R², m and n are defined the same as above.

Another embodiment of the present invention relates to a fragrancecomposition comprising the novel compounds provided above.

Another embodiment of the present invention relates to a fragranceproduct comprising the compounds provided above.

Another embodiment of the present invention relates to a method ofimproving, enhancing or modifying a fragrance formulation through theaddition of an olfactory acceptable amount of the novel compoundsprovided above.

These and other embodiments of the present invention will be apparent byreading the following specification.

DETAILED DESCRIPTION OF THE INVENTION

The (oxybis)dicyclohexane compounds represented by Formula I and FormulaII of the present invention are illustrated, for example, by followingexamples.

Those with skill in the art will recognize that the compounds of thepresent invention may have a number of isomers such as positionalisomers depending on the available starting materials. It is intendedherein that the compounds described herein include isomeric mixtures aswell as single isomers that may be separated using techniques known tothose having skill in the art. Suitable techniques includechromatography such as high performance liquid chromatography, referredto as HPLC, and particularly silica gel chromatography and gaschromatography trapping known as GC trapping. Yet, commercial productsare mostly offered as isomeric mixtures.

The preparation of the compounds of the present invention is detailed inthe Examples. Materials were purchased from Aldrich Chemical Companyunless noted otherwise.

The use of the compounds of the present invention is widely applicablein current perfumery products, including the preparation of perfumes andcolognes, the perfuming of personal care products such as soaps, showergels, and hair care products, fabric care products, air fresheners, andcosmetic preparations. The present invention can also be used to perfumecleaning agents, such as, but not limited to detergents, dishwashingmaterials, scrubbing compositions, window cleaners and the like.

In these preparations, the compounds of the present invention can beused alone or in combination with other perfuming compositions,solvents, adjuvants and the like. The nature and variety of the otheringredients that can also be employed are known to those with skill inthe art. Many types of fragrances can be employed in the presentinvention, the only limitation being the compatibility with the othercomponents being employed. Suitable fragrances include but are notlimited to fruits such as almond, apple, cherry, grape, pear, pineapple,orange, strawberry, raspberry; musk, flower scents such aslavender-like, rose-like, iris-like, carnation-like. Other pleasantscents include herbal and woodland scents derived from pine, spruce andother forest smells. Fragrances may also be derived from various oils,such as essential oils, or from plant materials such as peppermint,spearmint and the like.

A list of suitable fragrances is provided in U.S. Pat. No. 4,534,891,the contents of which are incorporated by reference as if set forth inits entirety. Another source of suitable fragrances is found inPerfumes, Cosmetics and Soaps, Second Edition, edited by W. A. Poucher,1959. Among the fragrances provided in this treatise are acacia, cassie,chypre, cyclamen, fern, gardenia, hawthorn, heliotrope, honeysuckle,hyacinth, jasmine, lilac, lily, magnolia, mimosa, narcissus, freshly-cuthay, orange blossom, orchid, reseda, sweet pea, trefle, tuberose,vanilla, violet, wallflower, and the like.

The compounds of the present invention can be used in combination with acomplementary fragrance compound. The term “complementary fragrancecompound” as used herein is defined as a fragrance compound selectedfrom the group consisting of 2-[(4-methylphenyl)methylene]-heptanal(Acalea), iso-amyl oxyacetic acid allylester (Allyl Amyl Glycolate),(3,3-dimethylcyclohexyl)ethyl ethyl propane-1,3-dioate (Applelide),(E/Z)-1-ethoxy-1-decene (Arctical),2-ethyl-4-(2,2,3-trimethyl-3-cyclo-penten-1-yl)-2-buten-1-ol (Bacdanol),2-methyl-3-[(1,7,7-trimethylbicyclo[2.2.1]hept-2-yl)oxy] exo-1-propanol(Bornafix), 1,2,3,5,6,7-hexahydro-1,1,2,3,3-pentamethyl-4H-inden-4-one(Cashmeran), trimethylcyclopentenylmethyloxabicyclooctane (Cassiffix),1,1-dimethoxy-3,7-dimethyl-2,6-octadiene (Citral DMA),3,7-dimethyl-6-octen-1-ol (Citronellol),3A,4,5,6,7,7A-hexahydro-4,7-methano-1H-inden-5/6-yl acetate (Cyclacet),3A,4,5,6,7,7A-hexahydro-4,7-methano-1H-inden-5/6-yl propinoate(Cyclaprop), 3A,4,5,6,7,7A-hexahydro-4,7-methano-1G-inden-5/6-ylbutyrate (Cyclobutanate),1-(2,6,6-trimethyl-3-cyclohexen-1-yl)-2-buten-1-one (Delta Damascone),3-(4-ethylphenyl)-2,2-dimethyl propanenitrile (Fleuranil),3-(O/P-ethylphenyl) 2,2-dimethyl propionaldehyde (Floralozone),tetrahydro-4-methyl-2-(2-methylpropyl)-2H-pyran-4-ol (Floriffol),1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta-gamma-2-benzopyran(Galaxolide), 1-(5,5-dimethyl-1-cyclohexen-1-yl)pent-4-en-1-one(Galbascone), E/Z-3,7-dimethyl-2,6-octadien-1-yl acetate (GeranylAcetate), α-methyl-1,3-benzodioxole-5-propanal (Helional),1-(2,6,6-trimethyl-2-cyclohexen-1-yl)-1,6-heptadien-3-one (Hexalon),(Z)-3-hexenyl-2-hydroxybenzoate (Hexenyl Salicylate, CIS-3),4-(2,6,6-trimethyl-2-cyclohexen-1-yl)-3-buten-2-one (Ionone α),1-(1,2,3,4,5,6,7,8-octahydro-2,3,8,8-tetramethyl-2-naphthalenyl)-ethan-1-one(Iso E Super), methyl 3-oxo-2-pentylcyclopentaneacetate (Kharismal),2,2,4-trimethyl-4-phenyl-butanenitrile (Khusinil),3,4,5,6,6-pentamethylhept-3-en-2-one (Koavone),3/4-(4-hydroxy-4-methyl-pentyl) cyclohexene-1-carboxaldehyde (Lyral),3-methyl-4-(2,6,6-trimethyl-2-cyclohexen-1-yl)-3-buten-2-one (MethylIonone γ), 1-(2,6,6-trimethyl-2-cyclohexen-1-yl) pent-1-en-3-one (MethylIonone α Extra, Methyl Ionone N), 3-methyl-4-phenylbutan-2-ol(Muguesia), cyclopentadec-4-en-1-one (Musk Z4),3,3,4,5,5-pentamethyl-11,13-dioxatricyclo[7.4.0.0<2,6>]tridec-2(6)-ene(Nebulone), 3,7-dimethyl-2,6-octadien-1-yl acetate (Neryl Acetate),3,7-dimethyl-1,3,6-octatriene (Ocimene), ortho-tolylethanol (Peomosa),3-methyl-5-phenylpentanol (Phenoxanol), 1-methyl-4-(4-methyl-3-pentenyl)cyclohex-3-ene-1-carboxaldehyde (Precyclemone B),4-methyl-8-methylene-2-adamantanol (Prismantol),2-ethyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol (Sanjinol),2-methyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol(Santaliff), Terpineol, 2,4-dimethyl-3-cyclohexene-1-carboxaldehyde(Triplal), decahydro-2,6,6,7,8,8-hexamethyl-2H-indeno[4,5-B]furan(Trisamber), 2-tert-butylcyclohexyl acetate (Verdox),4-tert-butylcyclohexyL acetate (Vertenex), acetyl cedrene (Vertofix),3,6/4,6-dimethylcyclohex-3-ene-1-carboxaldehyde (Vertoliff), and(3Z)-1-[(2-methyl-2-propenyl)oxy]-3-hexene (Vivaldie).

Complexity of odor notes refers to the presence of multiple and/or mixedbut defined odors rather than a single note or a few easily identifiablenotes. High levels of complexity are also assigned to compounds thatpossess ambiguous and somehow hard-to-define notes because of directcontribution or the many olfactive combinations of odors produced.Fragrance materials of high level complexity are considered havingunusual and high quality.

The term “alkyl” means a linear or branched saturated monovalenthydrocarbon, e.g., methyl, ethyl, propyl, 2-propyl, butyl (including allisomeric forms), pentyl (including all isomeric forms), hexyl (includingall isomeric forms), and the like. The term “alkenyl” means a linear orbranched unsaturated, aliphatic hydrocarbon containing at least onecarbon-carbon double bond. The term “alkylene” refers to bivalent alkyl.Examples include —CH₂—, —CH₂CH₂—, —CH₂CH₂CH₂—, —CH₂(CH₃)CH₂—,—CH₂CH₂CH₂CH₂—, and the like.

The terms “fragrance formulation”, “fragrance composition”, and “perfumecomposition” mean the same and refer to a consumer composition that is amixture of compounds including, for example, alcohols, aldehydes,ketones, esters, ethers, lactones, nitriles, natural oils, syntheticoils, and mercaptans, which are admixed so that the combined odors ofthe individual components produce a pleasant or desired fragrance. Thefragrance formulation of the present invention is a consumer compositioncomprising a compound of the present invention. The fragranceformulation of the present invention comprises a compound of the presentinvention and further a complementary fragrance compound as definedabove.

The term “fragrance product” means a consumer product containing afragrance ingredient that adds fragrance or masks malodor. Fragranceproducts may include, for example, perfumes, colognes, bar soaps, liquidsoaps, shower gels, foam baths, cosmetics, skin care products such ascreams, lotions and shaving products, hair care products for shampooing,rinsing, conditioning, bleaching, coloring, dyeing and styling,deodorants and antiperspirants, feminine care products such as tamponsand feminine napkins, baby care products such as diapers, bibs andwipes, family care products such as bath tissues, facial tissues, paperhandkerchiefs or paper towels, fabric products such as fabric softenersand fresheners, air care products such as air fresheners and fragrancedelivery systems, cosmetic preparations, cleaning agents anddisinfectants such as detergents, dishwashing materials, scrubbingcompositions, glass and metal cleaners such as window cleaners,countertop cleaners, floor and carpet cleaners, toilet cleaners andbleach additives, washing agents such as all-purpose, heavy duty, andhand washing or fine fabric washing agents including laundry detergentsand rinse additives, dental and oral hygiene products such astoothpastes, tooth gels, dental flosses, denture cleansers, dentureadhesives, dentifrices, tooth whitening and mouthwashes, health care andnutritional products and food products such as snack and beverageproducts. The fragrance product of the present invention is a consumerproduct that contains a compound of the present invention. The fragranceproduct of the present invention contains a compound of the presentinvention and further a complementary fragrance compound as definedabove.

The term “improving” in the phrase “improving, enhancing or modifying afragrance formulation” is understood to mean raising the fragranceformulation to a more desirable character. The term “enhancing” isunderstood to mean making the fragrance formulation greater ineffectiveness or providing the fragrance formulation with an improvedcharacter. The term “modifying” is understood to mean providing thefragrance formulation with a change in character.

The term “olfactory acceptable amount” is understood to mean the amountof a compound in a fragrance formulation, wherein the compound willcontribute its individual olfactory characteristics. However, theolfactory effect of the fragrance formulation will be the sum of effectof each of the fragrance ingredients. Thus, the compound of the presentinvention can be used to improve or enhance the aroma characteristics ofthe fragrance formulation, or by modifying the olfactory reactioncontributed by other ingredients in the formulation. The olfactoryacceptable amount may vary depending on many factors including otheringredients, their relative amounts and the olfactory effect that isdesired.

The amount of the compounds of the present invention employed in afragrance formulation varies from about 0.005 to about 70 weightpercent, preferably from 0.005 to about 50 weight percent, morepreferably from about 0.5 to about 25 weight percent, and even morepreferably from about 1 to about 10 weight percent. Those with skill inthe art will be able to employ the desired amount to provide desiredfragrance effect and intensity. In addition to the compounds of thepresent invention, other materials can also be used in conjunction withthe fragrance formulation to encapsulate and/or deliver the fragrance.Some well-known materials are, for example, but not limited to,polymers, oligomers, other non-polymers such as surfactants,emulsifiers, lipids including fats, waxes and phospholipids, organicoils, mineral oils, petrolatum, natural oils, perfume fixatives, fibers,starches, sugars and solid surface materials such as zeolite and silica.Some preferred polymers include polyacrylate, polyurea, polyurethane,polyacrylamide, polyester, polyether, polyamide,poly(acrylate-co-acrylamide), starch, silica, gelatin and gum Arabic,alginate, chitosan, polylactide, poly(melamine-formaldehyde),poly(urea-formaldehyde), or a combination thereof.

When used in a fragrance formulation these ingredients provideadditional notes to make a fragrance formulation more desirable andnoticeable, and add the perception of value. The odor qualities found inthese materials assist in beautifying and enhancing the finished accordas well as improving the performance of the other materials in thefragrance.

In addition, the compounds of the present invention are alsosurprisingly found to provide superior ingredient performance andpossess unexpected advantages in malodor counteracting applications suchas body perspiration, environmental odor such as mold and mildew,bathroom, and etc. The compounds of the present invention substantiallyeliminate the perception of malodors and/or prevent the formation ofsuch malodors, thus, can be utilized with a vast number of functionalproducts.

Examples of the functional products are provided herein to illustratethe various aspects of the present invention. However, they do notintend to limit the scope of the present invention. The functionalproducts may include, for example, a conventional room freshener (ordeodorant) composition such as room freshener sprays, an aerosol orother spray, fragrance diffusers, a wick or other liquid system, or asolid, for instance candles or a wax base as in pomanders and plastics,powders as in sachets or dry sprays or gels, as in solid gel sticks,clothes deodorants as applied by washing machine applications such as indetergents, powders, liquids, whiteners or fabric softeners, fabricrefreshers, linen sprays, closet blocks, closet aerosol sprays, orclothes storage areas or in dry cleaning to overcome residual solventnotes on clothes, bathroom accessories such as paper towels, bathroomtissues, sanitary napkins, towellets, disposable wash cloths, disposablediapers, and diaper pail deodorants, cleansers such as disinfectants andtoilet bowl cleaners, cosmetic products such as antiperspirant anddeodorants, general body deodorants in the form of powders, aerosols,liquids or solid, or hair care products such as hair sprays,conditioners, rinses, hair colors and dyes, permanent waves,depilatories, hair straighteners, hair groom applications such aspomade, creams and lotions, medicated hair care products containing suchingredients as selenium sulphide, coal tar or salicylates, or shampoos,or foot care products such as foot powders, liquids or colognes, aftershaves and body lotions, or soaps and synthetic detergents such as bars,liquids, foams or powders, odor control such as during manufacturingprocesses, such as in the textile finishing industry and the printingindustry (inks and paper), effluent control such as in processesinvolved in pulping, stock yard and meat processings, sewage treatment,garbage bags, or garbage disposal, or in product odor control as intextile finished goods, rubber finished goods or car fresheners,agricultural and pet care products such as dog and hen house effluentsand domestic animal and pet care products such as deodorants, shampoo orcleaning agents, or animal litter material and in large scale closed airsystems such as auditoria, and subways and transport systems.

Thus, it will be seen that the composition of the invention is usuallyone in which the malodor counteractant is present together with acarrier by means of which or from which the malodor counteractant can beintroduced into air space wherein the malodor is present, or a substrateon which the malodor has deposited. For example, the carrier can be anaerosol propellant such as a chlorofluoro-methane, or a solid such as awax, plastics material, rubber, inert powder or gel. In a wick-type airfreshener, the carrier is a substantially odorless liquid of lowvolatility. In several applications, a composition of the inventioncontains a surface active agent or a disinfectant, while in others, themalodor counteractant is present on a fibrous substrate. In manycompositions of the invention there is also present a fragrancecomponent which imparts a fragrance to the composition. The fragrancesstated above can all be employed.

Malodor counteracting effective amount is understood to mean the amountof the inventive malodor counteractant employed in a functional productthat is organoleptically effective to abate a given malodor whilereducing the combined intensity of the odor level, wherein the givenmalodor is present in air space or has deposited on a substrate. Theexact amount of malodor counteractant agent employed may vary dependingupon the type of malodor counteractant, the type of the carrieremployed, and the level of malodor counteractancy desired. In general,the amount of malodor counteractant agent present is the ordinary dosagerequired to obtain the desired result. Such dosage is known to theskilled practitioner in the art. In a preferred embodiment, when used inconjunction with malodorous solid or liquid functional products, e.g.,soap and detergent, the compounds of the present invention may bepresent in an amount ranging from about 0.005 to about 50 weightpercent, preferably from about 0.01 to about 20 weight percent, and morepreferably from about 0.05 to about 5 weight percent, and when used inconjunction with malodorous gaseous functional products, the compoundsof the present invention may be present in an amount ranging from about0.1 to 500 mg per cubic meter of air.

The following are provided as specific embodiments of the presentinvention. Other modifications of this invention will be readilyapparent to those skilled in the art. Such modifications are understoodto be within the scope of this invention. As used herein all percentagesare weight percent unless otherwise noted, ppm is understood to standfor parts per million, L is understood to be liter, mL is understood tobe milliliter, g is understood to be gram, Kg is understood to bekilogram, mol is understood to be mole, mmol is understood to bemillimole, psig is understood to be pound-force per square inch gauge,and mmHg be millimeters (mm) of mercury (Hg). IFF as used in theexamples is understood to mean International Flavors & Fragrances Inc.,New York, N.Y., USA.

Example I

Preparation of Oxybis(methylene))dicyclohexane (Structure 3)

Dibenzyl ether (600 g, 3 mol) was diluted with isopropanol (CH₃CHOHCH₃)(200 g) and placed in a 2-liter autoclave with ruthenium (IV) oxide(RuO₂) (2 g, 5 mmol equivalent). The autoclave was sealed, pressurizedwith nitrogen and vented. This step was repeated three times. Theautoclave was then flushed and vented three times with hydrogen. Theautoclave was subsequently pressurized with hydrogen (400 psig) andheated to 40° C. The reaction was aged for 2 hours, cooled and filtered.The crude product was distilled to afford the product(oxybis(methylene))dicyclohexane as a clear oil (570 g) having a boilingpoint of 120-124° C. at a pressure of 5 mmHg.

¹H NMR (500 MHz, CDCl₃): 3.17 (d, J=6.6 Hz, 4H), 1.61-1.86 (m, 10H),1.47-1.61 (m, 2H), 1.07-1.32 (m, 6H), 0.81-0.98 (m, 4H).

(Oxybis(methylene))dicyclohexane was described as having salicylate,sweet, floral, green, fresh and wintergreen notes.

Example II

Preparation of (2-(Benzyloxy)ethyl)benzene

2-Phenylethanol (300 g, 2.45 mol), sodium hydroxide (NaOH) (50% inwater, 104 g, 2.6 mol), tetrabutylammonium iodide ((CH₃CH₂CH₂CH₂)₄N(I))(17.51 g, 0.05 mol) and toluene (C₆H₅CH₃) were charged and heated to 80°C. Benzyl chloride (300 g, 2.4 mol) was fed in over a period of 4 hours.The reaction was aged for additional 5 hours and cooled. The aqueouslayer was removed. The remaining organic layer was washed with saturatedaqueous sodium chloride (NaCl) solution (twice with 300 mL each time)and fractionally distilled to provide (2-(benzyloxy)ethyl)benzene as aclear oil (450 g).

¹H NMR (400 MHz, CDCl₃): 7.41-7.66 (m, 10H), 4.76 (s, 2H), 3.94 (t,J=7.2 Hz, 2H), 3.20 (t, J=7.2 Hz, 2H)

Example III

Preparation of ((2-Cyclohexylethoxy)methyl)cyclohexane (Structure 4)

(2-(Benzyloxy)ethyl)benzene (152 g, 0.72 mol)) (obtained as above inEXAMPLE II) was placed in an autoclave with isopropanol ((CH₃)₂CHOH)(115 mL) and ruthenium (IV) oxide (0.6 g, 4.5 mmol). The autoclave wassealed, pressurized with hydrogen (400 psig) and heated to 45° C. Thereaction was aged for 4 hours and cooled. The crude product wasdistilled to afford ((2-cyclohexylethoxy)methyl)cyclohexane as a clearoil (120 g).

¹H NMR (500 MHz, CDCl₃): 3.39 (t, J=6.8 Hz, 2H), 3.17 (d, J=6.8 Hz, 2H),1.59-1.76 (m, 10H), 1.50-1.59 (m, 1H), 1.44 (q, J=6.8 Hz, 2H), 1.30-1.39(m, 1H), 1.08-1.28 (m, 6H), 0.84-0.94 (m, 4H)

Example IV

Diphenyl ether of the following structure was purchased from AldrichChemical Company.

Oxydicyclohexane (Structure 1) was prepared similarly according toEXAMPLE III from diphenyl ether.

¹H NMR (400 MHz, CDCl₃): 3.23-3.41 (m, 2H), 1.80-1.98 (m, 4H), 1.62-1.80(m, 4H), 1.38-1.62 (m, 2H), 0.88-1.38 (m, 10H)

(Benzyloxy)benzene of the following structure was also purchased fromAldrich Chemical Company.

(Cyclohexylmethoxy)cyclohexane (Structure 2) was prepared similarlyaccording to EXAMPLE III from (benzyloxy)benzene.

¹H NMR (500 MHz, CDCl₃): 3.18 (d, J=8.5 Hz, 2H), 3.09-3.14 (m, 1H),1.79-1.86 (m, 2H), 1.59-1.75 (m, 7H), 1.45-1.54 (m, 2H), 1.07-1.26 (m,8H), 0.81-0.90 (m, 2H)

(Oxybis(ethane-2,1-diyl))dibenzene of the following structure wasprepared similarly according to EXAMPLE II from (2-chloroethyl)benzeneand 2-phenylethanol.

¹H NMR (400 MHz, CDCl₃): 7.28-7.44 (m, 10H), 3.77 (t, J=7.2 Hz, 4H),3.00 (t, J=7.2 Hz, 4H)

(Oxybis(ethane-2,1-diyl))dicyclohexane (Structure 5) was preparedsimilarly according to EXAMPLE III from(oxybis(ethane-2,1-diyl))dibenzene.

¹H NMR (400 MHz, CDCl₃): 3.41 (t, J=6.8 Hz, 4H), 1.59-1.75 (m, 10H),1.43-1.48 (m, 4H), 1.31-1.42 (m, 2H), 1.08-1.29 (m, 6H), 0.84-0.96 (m,4H)

1-((Benzyloxy)methyl)-4-isobutylbenzene of the following structure wasprepared similarly according to EXAMPLE II from benzyl chloride and(4-isobutylphenyl)methanol.

¹H NMR (400 MHz, CDCl₃): 7.24-7.40 (m, 7H), 7.12 (d, J=8.0 Hz, 2H), 4.55(s, 2H), 4.52 (s, 2H), 2.47 (d, J=7.2 Hz, 2H), 1.77-1.96 (m, 1H), 0.90(d, J=6.7 Hz, 6H)

(((4-Isopropylcyclohexyl)methoxy)methyl)benzene of the followingstructure was prepared similarly according to EXAMPLE II from benzylchloride and (4-isopropylcyclohexyl)methanol.

¹H NMR (500 MHz, CDCl₃): 7.29-7.36 (m, 4H), 7.23-7.29 (m, 1H), 4.50 (s,65% of 2H), 4.49 (s, 35% of 2H), 3.39 (d, J=7.3 Hz, 65% of 2H), 3.27 (d,J=6.6 Hz, 35% of 2H), 0.89-1.97 (m, 11H), 0.77-0.88 (m, 6H)

1-((Cyclohexylmethoxy)methyl)-4-isopropylcyclohexane of the followingstructure was prepared similarly according to EXAMPLE III from(((4-isopropylcyclohexyl)methoxy)methyl)benzene.

¹H NMR (500 MHz, CDCl₃): 3.13-3.37 (m, 4H), 0.88-1.91 (m, 22H), 0.85 (d,J=6.9 Hz, 65% of 6H), 0.84 (d, J=6.9 Hz, 35% of 6H)

1-((Cyclohexylmethoxy)methyl)-4-isobutylcyclohexane of the followingstructure was prepared similarly according to EXAMPLE III from1-((benzyloxy)methyl)-4-isobutylbenzene.

¹H NMR (500 MHz, CDCl₃): 3.14-3.32 (m, 4H), 0.88-1.84 (m, 24H), 0.85 (d,J=6.6 Hz, 65% of 6H), 0.84 (d, J=6.3 Hz, 35% of 6H)

Example V

The fragrance properties of the above compounds were evaluated using (i)odor strength of 0 to 10, where 0=none, 1=very weak, 5=moderate,10=extremely strong; and (ii) level of complexity, where 0=none, 1=verylow, 5=moderate, 10=extremely high. Averaged scores are reported in thefollowing:

Compound Odor Profile Strength Complexity Diphenyl ether Floral, greenand 7 5 slightly woody Oxydicyclohexane Floral, green, sweet and 6 6(Structure 1) herbal. A solventy quality developed when drying(Benzyloxy)benzene Lime-/moss-like, effervescent, 6 4 sweet and herbalbut synthetic and artificial. A metallic note developed when drying(Cyclohexylmethoxy)cyclohexane Floral, green, effervescent and 4 4(Structure 2) fruity but dirty, metallic, synthetic and unpleasantDibenzyl ether Floral, fruity and sweet but 4 3 synthetic and unpleasantOxybis(methylene))dicyclohexane Unique and unusual salicylate 7 9(Structure 3) note. Floral, green, sweet, soft-feel, fresh, elegant-feeland wintergreen (2-(Benzyloxy)ethyl)benzene Floral and green butsynthetic 4 4 ((2-Cyclohexylethoxy)methyl) Floral and green but oily, 43 cyclohexane dirty and unpleasant (Structure 4)(Oxybis(ethane-2,1-diyl))dibenzene Moss-like and green but weak 2 2 andthin (Oxybis(ethane-2,1-diyl))dicyclohexane Solventy, weak and thin 2 2(Structure 5) 1-((Benzyloxy)methyl)-4- Nutty and slightly woody. An 4 4isobutylbenzene oily character developed later(((4-Isopropylcyclohexyl)methoxy) Fruity, artificial and synthetic 2 2methyl)benzene with a chlorine-like quality1-((Cyclohexylmethoxy)methyl)-4- Woody, animalic, fatty, 1 1isopropylcyclohexane heavy-feel, weak and thin1-((Cyclohexylmethoxy)methyl)-4- Floral, green, slightly woody 3 4isobutylcyclohexane and synthetic. A dirty note developed when drying.

Oxybis(methylene))dicyclohexane exhibited unique and particularlydesirable salicylate note. Its odor profile is strong and complex,superior to all other analog compounds. Such advantageous properties areunexpected.

Example VI Establishment of Malodor Models:

The sweat, mold/mildew, bathroom and smoke malodor models were preparedbased on Applicants' proprietary formulations for assessing theeffectiveness of various malodor counteractants.

Preparation of Test Samples:

Two aluminum dishes were placed in an 8 oz glass jar. A malodor materialwas pipetted into one aluminum dish, and(oxybis(methylene))dicyclohexane (prepared above in EXAMPLE I) dilutedin a solvent (1%) or a solvent alone control was pipetted into the otheraluminum dish. The jar was then capped and the samples were allowed toequilibrate for one hour before the testing.

Testing Procedure:

Test samples were presented in a blind and random order to 15-18internal panelists (consisting of men/women with an age range of 25 to55). However, different odor samples were arranged in an alternativeorder (for example, sweat, mold/mildew, sweat, mold/mildew, and etc.).

The panelists were instructed to take the steps of i) sniff jarscontaining only the malodor materials for familiarization prior to thetesting; ii) uncap a jar; iii) place their noses at a distance of about3-4 inches above the opening; iv) take short sniffs for 3 seconds; andv) enter a rating of overall intensity and malodor intensity on ahandheld computer.

The overall and malodor intensity was rated using the Labeled MagnitudeScale (LMS) [Green, et al., Chemical Senses, 21(3), June 1996, 323-334].Percent malodor reduction (“% MOR”) represents the perceived reductionin mean malodor intensity of the sample containing the malodor in thepresence of a malodor counteractant relative to the negative control(Malodor Alone).

Results and Discussion:

The mean ranks of the malodor coverage for the above test were asfollows:

Compound (1%) Malodor % MOR (oxybis(methylene))dicyclohexane Sweat 39.74Mold/Mildew 49.73 Bathroom 56.90 Smoke 21.18

(Oxybis(methylene))dicyclohexane was demonstrated effective incounteracting various types of malodors.

1. A fragrance composition comprising an olfactory acceptable amount ofa compound of Formula I:

wherein R¹ and R² are identical or different and each is a C₁-C₃alkylene group; R³ and R⁴ are identical or different and each ishydrogen or methyl located in any positions of the ring to which theyare attached; and wherein m and n are identical or different and each isan integer of 0 or
 1. 2. The fragrance composition of claim 1, whereinthe compound is of Formula II:

wherein R¹ and R² are identical or different and each is a C₁-C₃alkylene group; and wherein m and n are identical or different and eachis an integer of 0 or
 1. 3. The fragrance composition of claim 2,wherein the compound is selected from the group consisting of:oxydicyclohexane; (cyclohexylmethoxy)cyclohexane;(oxybis(methylene))dicyclohexane;((2-cyclohexylethoxy)methyl)cyclohexane;(oxybis(ethane-2,1-diyl))dicyclohexane;(oxybis(propane-3,1-diyl))dicyclohexane;4,4′-(oxybis(methylene))bis(methylcyclohexane);4,4′-(oxybis(ethane-2,1-diyl))bis(methylcyclohexane);1,1′-(oxybis(methylene))bis(1-methylcyclohexane);(oxybis(ethane-1,1-diyl))dicyclohexane; and a mixture thereof.
 4. Thefragrance formulation of claim 1, wherein the olfactory acceptableamount is from about 0.005 to about 50 weight percent of the fragranceformulation.
 5. The fragrance formulation of claim 1, wherein theolfactory acceptable amount is from about 0.5 to about 25 weight percentof the fragrance formulation.
 6. The fragrance formulation of claim 1,wherein the olfactory acceptable amount is from about 1 to about 10weight percent of the fragrance formulation.
 7. The fragranceformulation of claim 1 further comprising a polymer.
 8. The fragranceformulation of claim 7, wherein the polymer is selected from the groupconsisting of polyacrylate, polyurea, polyurethane, polyacrylamide,polyester, polyether, polyamide, poly(acrylate-co-acrylamide), starch,silica, gelatin and gum Arabic, alginate, chitosan, polylactide,poly(melamine-formaldehyde), poly(urea-formaldehyde) and a combinationthereof.
 9. A method of improving, enhancing or modifying a fragranceformulation through the addition of an olfactory acceptable amount of acompound of Formula I:

wherein R¹ and R² are identical or different and each is a C₁-C₃alkylene group; R³ and R⁴ are identical or different and each ishydrogen or methyl located in any positions of the ring to which theyare attached; and wherein m and n are identical or different and each isan integer of 0 or
 1. 10. The method of claim 9, wherein the compound isof Formula II:

wherein R¹ and R² are identical or different and each is a C₁-C₃alkylene group; and wherein m and n are identical or different and eachis an integer of 0 or
 1. 11. The method of claim 10, wherein thecompound is selected from the group consisting of: oxydicyclohexane;(cyclohexylmethoxy)cyclohexane; (oxybis(methylene))dicyclohexane;((2-cyclohexylethoxy)methyl)cyclohexane;(oxybis(ethane-2,1-diyl))dicyclohexane;(oxybis(propane-3,1-diyl))dicyclohexane;4,4′-(oxybis(methylene))bis(methylcyclohexane);4,4′-(oxybis(ethane-2,1-diyl))bis(methylcyclohexane);1,1′-(oxybis(methylene))bis(1-methylcyclohexane);(oxybis(ethane-1,1-diyl))dicyclohexane; and a mixture thereof.
 12. Afragrance product containing the fragrance formulation of claim
 1. 13.The fragrance product of claim 12, wherein the fragrance product isselected from the group consisting of a perfume, a cologne, toiletwater, a cosmetic product, a personal care product, a fabric careproduct, a cleaning product and an air freshener, a bar soap, a liquidsoap, a shower gel, a foam bath, a cosmetic, a skin care product, a haircare product, a deodorant, an antiperspirant, a feminine care product, ababy care product, a family care product, a fabric product, an air careproduct, a fragrance delivery system, a cosmetic preparation, a cleaningagent, a disinfectant, a washing agent, a dental and oral hygieneproduct, a health care and nutritional product and a food product. 14.The fragrance product of claim 13, wherein the cleaning product isselected from the group consisting of a detergent, a dishwashingmaterial, a scrubbing composition, a glass cleaner, a metal cleaner, acountertop cleaner, a floor cleaner, a carpet cleaner, a toilet cleanerand a bleach additive.
 15. The fragrance product of claim 13, whereinthe washing agent is selected from the group consisting of a laundrydetergent and a rinse additive.
 16. A method of counteracting a malodorin an air space or a substrate comprising the step of introducing to theair space or the substrate a composition comprising a compound ofFormula I:

wherein R¹ and R² are identical or different and each is a C₁-C₃alkylene group; R³ and R⁴ are identical or different and each ishydrogen or methyl located in any positions of the ring to which theyare attached; and wherein m and n are identical or different and each isan integer of 0 or
 1. 17. The method of claim 16, wherein the compoundis of Formula II:

wherein R¹ and R² are identical or different and each is a C₁-C₃alkylene group; and wherein m and n are identical or different and eachis an integer of 0 or
 1. 18. The method of claim 17, wherein thecompound is selected from the group consisting of: oxydicyclohexane;(cyclohexylmethoxy)cyclohexane; (oxybis(methylene))dicyclohexane;((2-cyclohexylethoxy)methyl)cyclohexane;(oxybis(ethane-2,1-diyl))dicyclohexane;(oxybis(propane-3,1-diyl))dicyclohexane;4,4′-(oxybis(methylene))bis(methylcyclohexane);4,4′-(oxybis(ethane-2,1-diyl))bis(methylcyclohexane);1,1′-(oxybis(methylene))bis(1-methylcyclohexane);(oxybis(ethane-1,1-diyl))dicyclohexane; and a mixture thereof.